CN101068043A - 用于布置在蓄电池中的隔片和蓄电池 - Google Patents

用于布置在蓄电池中的隔片和蓄电池 Download PDF

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CN101068043A
CN101068043A CNA2007101077049A CN200710107704A CN101068043A CN 101068043 A CN101068043 A CN 101068043A CN A2007101077049 A CNA2007101077049 A CN A2007101077049A CN 200710107704 A CN200710107704 A CN 200710107704A CN 101068043 A CN101068043 A CN 101068043A
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P·克里策
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Carl Freudenberg KG
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Abstract

本发明涉及一种用于布置在蓄电池中的隔片，它包括至少一个第一层和至少一个第二层，其中，所述层设计成无纺布，针对本发明的目的，提供一种蓄电池，在毫无问题地制造之后，该蓄电池保证在具有大功率的同时具有长的使用寿命，其特征为，所述第一层具有其平均直径大于所述第二层的纤维的平均直径的纤维。

Description

用于布置在蓄电池中的隔片和蓄电池
技术领域
本发明涉及一种用于布置在蓄电池中的隔片，它包括至少一个第一层和至少一个第二层，其中，所述层作为无纺布构成。此外，本发明还涉及一种包含一隔片的蓄电池。
背景技术
在可充电的、采用含水电解液的蓄电池系统中，电解液在蓄电池充电或放电时参与化学反应。在已知的蓄电池系统中，必须有足够大的电解液储存器，该储存器通常由无纺布隔片提供。为此，无纺布隔片需要有足够大的容积。因此，减少隔片的厚度只有在某些条件下可以实现。
在锂蓄电池中，由于其高的电化学电位，不采用含水电解液，这是因为这种电解液会电解分解。在这种类型的蓄电池中，采用氧化稳定的有机液体如碳酸丙烯，这种液体在充电/负载(Laden)或放电时不参与化学反应。所述液体只担任运输离子的功能，从而在这种蓄电池系统中，隔片可以非常薄。  隔片的厚度只受到机械强度尤其是抗穿刺性(Durchstoβfestigkeit)的限制。
耐大电流的蓄电池，即所谓的“高能蓄电池”优选用在电动工具中。这种类型的蓄电池要求有高孔隙度的隔片。提高隔片的孔隙度提高了蓄电池的功率，因而提高了其中采用这种蓄电池的工具的功率。
从现有技术已知的隔片在其孔隙度及其机械强度上都有明显的缺点。
发明内容
因此，本发明的目的是，即提供一种蓄电池，在没有问题的制造之后，这种蓄电池在大功率的同时确保有长的使用寿命。
本发明通过权利要求1的特征来实现所述目的。据此，隔片的特征为，第一层有平均直径大于第二层的纤维的平均直径的纤维。
按照本发明，在第一步中获知，从现有技术已知的隔片常常没有足够的稳定性。在第二步中获知，可以这样来提高隔片的稳定性，即至少一个层起支承层的作用。按照本发明，支承层具有直径比第二层的大的纤维。按照本发明，第二层具有这样的纤维结构，该结构可在具有小的小孔隙尺寸的同时保证非常高的孔隙度。只要能够实现一种具有稳定的隔片的蓄电池，则就可以毫无问题地制造蓄电池。由于隔片的稳定性，不仅可以实现毫无问题地制造蓄电池，还可以实现蓄电池长的使用寿命。最后，可通过按照本发明的隔片形成高的孔隙度，从而能实现高功率的蓄电池。
因此，可以实现所述目的。
第一层可以包括具有大于2μm的平均直径的纤维。第二层可以包括具有小于900nm的平均直径的纤维。这种具体的构形一方面允许形成足够稳定的支承层，该支承层使第二层稳定。因此，第二层几乎不必满足任何力学要求，并可以与第一层无关地在孔隙度和纤维结构上对第二层调节。已知过大的孔隙尺寸会导致蓄电池的沉淀/故障。由于过大的孔隙可产生导电的连晶/共生(Durchwachsung)，即所谓的树枝状晶体(Dendrite)，并导致短路。采用纳米纤维，允许在形成很小的孔隙直径的情况下，形成有很高的孔隙度的无纺布，从而可以有效地避免连晶。
隔片可以具有三层的结构，其中，两个第一层在其之间包夹第二层。这种具体的构形允许隔片有特别稳定的结构，因为，包括纳米纤维的层夹层式地位于两个稳定的支承层之间。这种具体的构形实现了隔片特别高的抗穿刺性。
隔片可以具有三层的结构，其中，两个第二层在其之间包夹第一层。这种具体构形的隔片在有足够的稳定性的同时具有很高的孔隙度。第二层夹层式地在其之间包夹第一层，第一层起稳定的支承层的作用。
在前面所述的构形中，可以设想，各个层彼此粘合。粘合是一种廉价的连接。
此外可以设想，所述层通过化学反应如交联彼此连接。由此，实现各层之间特别稳定并且是几乎是不能分开的连接。
此外可以设想，所述层通过焊接例如通过电子束、激光或超声彼此焊在一起。这种连接形式可有选择地在整个面上或点状地进行。根据各层彼此的连接在整个面上还是点状地进行，可以调节复合层(Lagenverbund)的弹性和弯曲强度。
最后可以设想，所述层通过机械方法如喷水加固彼此连接。喷水加固允许无端纤维或短纤维扭结/交织(Verschlingung)，而不必使用附加的连接材料。由此，可以实现制造单纯品种的隔片，这种隔片可以毫无问题地回收处理。可以有效地放弃使用会损伤蓄电池的粘合材料或其它连接材料。
至少一个层可以分层构造。在这种背景下可以设想，每个第一层或每个第二层本身设计成复合层。这里可以设想，每个层由具有不同的化学组分的纤维组成。此外可以设想，一第一层和一第二层都有一渐变的构造。渐进的构造可以理解为，沿任何一个方向都形成纤维直径的梯度。通过这种构造可以实现，使污垢颗粒被具有较粗的孔隙度的层接纳，从而保护具有较细孔隙度的层不受损伤。随着时间的推移，较粗层的堵塞使得具有的孔隙度较粗的层得到越来越小的孔隙，并由此可实现对较细的颗粒的过滤。
至少一个层可以包括用这样一种聚合物制成的纤维，该聚合物的熔点至少为160℃。由现有技术已知一种隔片，它在120℃以上的温度下就开始熔化。在更高的温度下，整个隔片都会熔化，从而产生所谓的“熔化效应(Melt-Down-Effekt)”。这种效应导致蓄电池的危险状态，因为隔片材料甚至在低于熔点的温度下就已经有明显的热收缩。这可造成蓄电池负载/充电不同的电极暴露。一旦电极暴露，就不再能实现蓄电池的安全运行。
第一层可包含用聚酯制成的纤维。聚酯的特征在于，高的温度稳定性。由聚酯制成的无纺布在200℃的温度下在20分钟的加热时间之后具有小于2％的热收缩率。
第二层可包含由聚烯烃制成的纤维。在温度升高时，采用聚烯烃允许孔隙有确定的封闭。如果一个由聚酯制成的层与一个由聚烯烃制成的层组合，则获得隔片的温度稳定性并由此获得隔片的机械强度，其中，可以同时实现孔隙确定的封闭。因此可以确定地调节所谓的切断效应(Abschalteffekt)。切断效应提高了蓄电池的可靠性，从而可以通过某些特殊的聚烯烃材料的熔化而应付电池的超载或短路。
在此背景之下，特别具体地第二层可以包括由聚乙烯制成的纤维。
隔片可以具有5-35g/m2的面密度。从这个范围选择面密度可以保证，隔片有足够的强度，从而可以进行机加工。在稳定性上已经证明特别是5-20g/m2的范围是更为常用的。
隔片的特征可以是10-35μm的厚度。从这个范围选择厚度可以保证，隔片可以提供足够大的容积以接纳电解液，此外还可以承担机械载荷。在厚度尽可能小同时的接纳能力上，已经证明10-25g/m2的范围特别有利。
隔片可以有一35-80％的孔隙度。这种具体的构形允许将隔片用在耐大电流的蓄电池中。在蓄电池的有效功率上，已经证明45-80％的范围特别有利。从现有技术已知一种膜，这种膜在挤出之后直接拉伸。这种膜具有通常明显低于这里所要求的范围的孔隙度。
隔片可具有最大4μm的孔隙尺寸。从这个范围选择小孔尺寸可以保证不会发生隔片的连晶。所述连晶是指所形成的、并造成短路的树枝状晶体结构。通过从上述范围选择最大的孔隙尺寸，可有效防止连晶的形成。如果孔隙尺寸(孔隙直径)最大为2μm，这可实现特别小的连晶(速)率。
隔片可以具有至少8N/(5cm)的纵向最大拉力。这种具体的构形保证毫无问题的可加工性。所述最大拉力还保证，隔片材料可以用机器卷绕。具有上述最大拉力的隔片材料还具有高的抗穿刺性。
隔片可以在加热至140℃30分钟以后具有小于5％的横向热收缩。这种隔片允许即使在高温时或在较长的运行时间后也可使用蓄电池。通过采用上述隔片可以保证，电极几乎不会暴露。因此，即使在较长的运行时间以后和在高温下，也能保证蓄电池运行的可靠性。
此外，上述目的还可通过一种包括这里所述类型隔片的蓄电池来实现。
为了避免重复，关于创造性可参考这种隔片的说明。
现在有各种以有利的方式实施和改进本发明的教导的可能性。为此，一方面可参见并列的独立权利要求的从属权利要求，另一方面可参考下面根据附表对本发明的优选实施例的说明。结合本发明的优选实施例的说明，根据附表，总体上还说明了本发明教导的优选实施形式和改进方案。
具体实施方式
表的说明：
表1示出两层隔片的具体实施例。
在表1中示出材料C1至C19。所述材料由两层A和B组成。
作为层A，即作为第一层，采用下列无纺布：
A1：湿铺放(naβlegen)的、热结合的聚酯无纺布。该无纺布有3-4μm之间的平均纤维直径，8g/m2的面密度和13μm的厚度。
A2：湿铺放的、热结合的聚酯无纺布。此无纺布有3-4μm之间的平均纤维直径，13g/m2的面密度和24μm的厚度。
A3：湿铺放的、用丙烯酸类粘合剂化学结合的、由聚丙烯腈纤维制成的无纺布，有12g/m2的面密度和24μm的厚度。
A4：热加固的聚酯纺粘型无纺布。它具有平均纤维直径约为9μm的纤维。该无纺布具有14g/m2的面密度和26μm的厚度。
A5：聚丙烯喷熔型无纺布，有13g/m2的面密度和26μm的厚度。
A6：热加固的聚酯干式无纺布。它具有平均纤维直径约为12μm的纤维。该无纺布具有17g/m2的面密度和26μm的厚度。
对于作为第二层起作用的层B，采用下列材料：
B1：在第一层上施加由二氯甲烷静电纺制的聚碳酸酯纤维。该纤维有小于800μm的平均直径。第二层有2-10g/m2的面密度。
B2：在第一层上由N-甲基-吡咯烷酮静电纺制聚砜纤维和聚醚砜纤维。所述纤维有小于800μm的平均直径。第二层有5g/m2的面密度。
B3：在第一层上施加由氯乙烯静电纺制的聚乙烯纤维。该纤维有小于800μm的平均直径。第二层有3-5g/m2的面密度。
B4：由六氟异丙醇静电纺制包括聚对苯二甲酸乙二醇酯的纤维，并将其施加在第一层上。该纤维有小于800μm的平均直径。第二层有3g/m2的面密度。
B5：由N，N-二甲基乙酰胺静电纺制Polyvinyledenfluorid(聚偏二氟乙烯)纤维，并将其铺放到第一层上。该纤维有小于800μm的平均直径。第二层有3-5g/m2的面密度。
B6：由全氯乙烯静电纺制聚丙烯纤维，并将其铺放到第一层上。该纤维有小于800μm的平均直径。第二层有3-5g/m2的面密度。
B7：由全氯乙烯静电纺制聚苯乙烯纤维，并将其铺放到第一层上。该纤维有小于800μm的平均直径。第二层有3-5g/m2的面密度。
B8：由二甲基甲酰胺静电纺制聚丙烯腈纤维，并将其铺放到第一层上。该纤维有小于800μm的平均直径。第二层有3-5g/m2的面密度。
B9：由二甲基甲酰胺静电纺丝聚醚酰亚胺纤维，并将其铺放到第一层上。该纤维有小于800μm的平均直径。第二层有3-5g/m2的面密度。
B10：由熔体纺制“海岛(island in the sea)”型的聚丙烯纤维和聚酯纤维。该纤维有小于800μm的平均直径。第二层有3g/m2的面密度。
B11：按喷熔法纺制聚偏二氟乙烯纤维。该纤维具有约600μm的平均直径。第二层有5g/m2的面密度。
从表1可以看出，材料C1至C19设计成两个层的复合结构。这里，例如材料C5由层A1和层B2的复合层组成，其中，层A1起第一层的作用，而层B2起第二层的作用。层A1起支承层的作用，并使复合层稳定。
表1的第3栏用g/m2示出层结合的总密度。在第3栏中在括号中列出，总密度的哪一部分归于第一层或第二层。表的第4栏给出复合层的厚度。第5栏为复合层的孔隙度，而第6栏为最大孔隙尺寸。在第7栏中用单位N/5(cm)给出最大纵向拉力。最后，第8栏给出关于横向热收缩率的数据，其中，该数据用％给出。通过将试件加热到180℃持续30分钟而确定热收缩率。
在按照本发明的教导的其它有利的实施形式和改进方案上，一方面参考说明书的概述部分，另一方面参考后附的权利要求。
最后特别应该强调，在前面只是任意选择的实施例只用于说明本发明的教导，该教导不能限于所述实施例。
  材料   层     总密度(g/m2)   厚度(um)     孔隙度(％)  最大孔隙尺寸(μm)   最大拉力(N/5cm)  横向热收缩率(％)*
  C1   A1+B1     10(8+2)     17     60     3.2     14    在180℃时＜2
  C2   A1+B1     12(8+4)     21     57     1.8     14    在180℃时＜2
  C3   A1+B1     14(8+6)     25     57     1.2     14    在180℃时＜2
  C4   A1+B1     18(8+10)     33     58     1.0     15    在180℃时＜2
  C5   A1+B2     13(8+5)     21     53     1.5     14    在180℃时＜2
  C6   A1+B3     13(8+5)     22     50     1.7     14    在180℃时＜2
  C7   A1+B4     13(8+5)     21     56     1.6     14    在180℃时＜2
  C8   A1+B5     13(8+5)     22     64     1.5     14    在180℃时＜2
  C9   A1+B6     13(8+5)     23     53     1.8     14    在180℃时＜2
  C10   A1+B7     13(8+5)     22     53     1.5     14    在180℃时＜2
  C11   A1+B8     13(8+5)     22     58     1.5     14    在180℃时＜2
  C12   A1+B9     13(8+5)     21     54     1.4     14    在180℃时＜2
  C13   A1+B10     13(8+5)     21     53     1.4     14    在180℃时＜2
  C14   A2+B2     18(13+5)     27     50     1.6     14    在180℃时＜2
  C15   A3+B2     17(12+5)     32     56     1.6     14    在180℃时＜2
  C16   A4+B2     19(14+5)     33     57     1.7     14    在180℃时＜2
  C17   A5+B2     21(16+5)     32     42     1.8     14    在180℃时＜10**
C18 A8+B2 22(17+5) 32 49 2.9 14 在180℃时＜2
  C19   A1+B11     13(8+5)     28     69     3.6     14    在180℃时＜2
                                                               表1

Claims (13)

1、用于布置在蓄电池中的隔片，该隔片包括至少一个第一层和至少一个第二层，其中，所述层设计成无纺布，其特征为，所述第一层包括其平均直径大于第二层纤维的平均直径的纤维。
2、如权利要求1的隔片，其特征为，所述第一层包括具有大于2μm的平均直径的纤维，所述第二层包括具有小于800μm的平均直径的纤维。
3、如权利要求1的隔片，其特征为，具有三层结构，其中，两个第一层在其之间包夹第二层。
4、如权利要求1的隔片，其特征为，具有三层结构，其中，两个第二层在其之间包夹第一层。
5、如权利要求1至4之一的隔片，其特征为，至少一个层具有层式的结构。
6、如权利要求1至5之一的隔片，其特征为，至少一个层包括由熔点至少为160℃的聚合物制成的纤维。
7、如权利要求1至6之一的隔片，其特征为，具有5-35g/m2，特别优选为5-20g/m2的面密度。
8、如权利要求1至7之一的隔片，其特征为，具有10-35μm，特别优选为10-25μm的厚度。
9、如权利要求1至8之一的隔片，其特征为，具有35-80％，特别优选为45-80％的孔隙度。
10、如权利要求1至9之一的隔片，其特征为，具有4μm，特别优选为2μm的最大孔隙尺寸。
11、如权利要求1至10之一的隔片，其特征为，具有至少为8N/(5cm)的纵向最大拉力。
12、如权利要求1至11之一的隔片，其特征为，具有在加热到140℃30分钟时小于5％的横向热收缩率。
13、包括如前述权利要求之一的隔片的蓄电池。
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